ii J. App]. Chem.

, 3, JUII~, 1953

Inl

WO

We are exhibiting at
rea
wit
the British Instrument Industries

hoi
Exhibition at Olympia.

Ill:
from 30th June to 11th July.
as 1
on STAND No. IDE.

cor
lOO-litre capacity
electrically heated
Reaction Units G
E
In
red
It is Th
pro

bas

better
in car

glass

Striking significance attaches to the fact that the
manufacturer who once tries industrial plant in
glass never reverts to metal. Experience of the
advantages of all-glass plant is the best of all adver­
tisements for that product. Take the Reaction Units
illustrated. It is obvious how qUickly they can be
assembled or dismantled, how readily they can be
cleaned. The installations are compact, light in
weight and give perfect visual control of the wor~
they do. Glass eliminates the risk of corrosion
and bri ngs laboratory standards of purity to lar~e
scale production.

QUICKFIT & QUARTZ LTD tl

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h
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o
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HEAD OFFICE: I, Albemarle St., London, W.I J
 DAROUX-PRODUCTION OF ACETIC ANHYDRIDE

PRODUCTION OF ACETIC ANHYDRIDE FROM ACETONE*

By W. GERARD DAROVX

The pilot-plant process evaluation and full-scale design for the production of acetic anhydride from
acetone are described. Pasic economics and alternative processes are briefly discussed.

Introduction
Acetic anhydride is a basic raw material for the cellulose acetate manufacturer and the bulk of
world production is used for this purpose. Minor outlets for the chemical include acetylation
reactions in organic chemistry, e.g. the production of aspirin. The reactivity of acetic anhydride
with water is also employed in the manufacture of hexamethylenetetramine explosives. There is,
however, a striking constancy in the ratio of acetic anhydride production to cellulose acetate output!
in peace-time conditions. This shows quite clearly the importance of cellulose acetate manufacture
as the main outlet for acetic anhydride.
It is characteristic of this cellulose-acetylation reaction that about half the acetic anhydride
consumed is reconverted into acetic acid, in accordance with the simple scheme shown in Fig. I.
Each mole of acetic anhydride used for
acetylation produces, in round figures, one mole
of surplus acetic acid, which must be reconverted
into the raw material.
The modern method of reconverting the acetic
acid into anhydride is the acid-cracking process, in
which catalysed vapour-phase cracking of acid is
FIG. 1. Basic scheme for cellulose acetylation much employed to give keten and water.s The
keten is then absorbed in acetic acid to give
anhydride, which is returned to the acetate process.
In this way the cellulose acetate manufacturer avoids the production of excess of acetic acid and
reduces his net anhydride requirement to about o· 7 ton of anhydride per ton of cellulose acetate.
This is sufficient to supply the acetyl content of the cellulose acetate flake and to make up the
process losses.
The net amounts of acetic anhydride required may then be produced from any of the following
basic raw materials, all of which have been employed on a large commercial scale: (a) calcium
carbide or acetylene, (b) ethanol, or (c) isopropanol.
The processes are shown diagrammatically in Fig. 2.

RAW MATEAIAL rNTERAlEDIATE$

I METHANE
AcET rc
ANHYDRIDE
_ _ _ _~ and lor
I ETHANOL
ACID
AC ETIC
ACID

FIG. 2. Outline Of processes for the production of acetic anhydride

General economics
In the immediate post-war period a study of the methods of producing anhydride indicated
that isopropanol gave the greatest promise as a basic raw material for economical anhydride
production in the United Kingdom. Calcium carbide suffered from the major disadvantage of
high power-cost and high coal-prices. The developments of methane cracking to produce acetylene
* Read before a joint meeting of the Chemical Engineering Group and the Institution of Chemical Engineers.
on 31 March, 1953

J. appl, Chern., 3, June, 1953 F

 DAROUX-PRODUCTlON OF ACETIC ANHYDRIDE

did not give high hopes of a specific cheap process. Ethanol based on molasses, a commodity
which fluctuates very much in price, appeared in the long view to be faced with severe competition
from petro-chemical processes, which were at that time developing rapidly.
It was then thought that the best hope of obtaining cheap anhydride lay in exploitation of
the synthetic ethanol and isopropanol arising as by-products from the olefins produced in oil-cracking.
The cost studies which were made at the time were very much hampered by the difficulty of assessing
the true value of the unsaturated hydrocarbons produced as by-products and the real cost of the
marginal facilities required to convert them into shippable products. This is a difficulty which
always arises when a variety of products are being made in a single process. The costs may be
loaded on one or the other product according to the circumstances.
The following main conclusions stood out clearly from the mass of economic detail: First,
the cracking of crude oil mainly for the production of a single aliphatic alcohol, such as ethanol or
isopropanol, was not likely to be economic, owing to the very heavy weighting of capital investment.
Secondly, isopropanol was more likely to settle down, under conditions of large-scale production
and free competition, to a basic cost and selling price substantially less than that of ethanol. Under
these conditions, acetone, cheaply and simply produced by isopropanol dehydrogenation, would be
a suitable material for anhydride synthesis.
These conclusions led to our interest in acetone-cracking and its process evaluation.

Basic reaction and chemistry

It is well known that acetone may be thermally decomposed in a copper or silica tube according
to the reaction a, 4, 5 CH:J • CO· CH 3 -+ CH 4 -:-- CH 2 : CO, and that keten itself may decompose to
ethylene and carbon monoxide thus:" 2CH 2·.CO --'~ C 2H 4 ~- 2CO. Other possible reactions are:
dehydrogenation, which has been observed in our own work, CH 3 . CO . CH 3 ... 3H2 -+- CO ~- 2C;
,?

and polymerization of keten to diketen and high polymers, sometimes with the elimination of carbon
dioxide. \
The main cracking reaction is slightly endothermic, to the extent of about 29,000 B.Th.U .jlb -rnol.,
a figure which is very small compared with the sensible heat of the cracking stock, which must be
heated to 1200-1500" F. It has also been shown in early experiments that the molar yield of keten
diminishes with increasing conversion per pass and that at over 50% conversion the yields
become uneconomic. Nickel and iron have been reported to promote the dehydrogenation of
acetone. Hinshelwood & Hutchison? have found that the thermal decomposition of acetone is
first-order and homogeneous, though their conclusions have been questioned by Taylor."
Keten may be smoothly fixed in acetic acid to produce acetic anhydride, a reaction which
evolves about 42,000 B.Th.U.jlb.-mol.
The published data on the cracking process are of only slight value to the designer, and it was
therefore necessary to investigate the reaction on a pilot and laboratory scale before a full-scale plant
could be worked out. This work was confined largely to the cracking step, as it appeared that the
absorption, recycling and recovery units could be designed by normal methods after laboratory
checking of the physical data.

Pilot plant
The chief problems investigated on the pilot plant were the general feasibility of the cracking
reaction, materials of construction of the cracking tube and the conversion-selectivity relationship.
An outline flow-sheet of the pilot plant is shown in Fig. 3. It consists of a steam-heated acetone
vaporizer, a preheating coil and cracking coil separately gas-fired, together with quench, absorption
and distillation units. The cracked products were rapidly quenched with a recycle liquor which
contained acetic anhydride and free acetic acid. This fixes the keten as rapidly as possible after
its generation in the furnace. Unconverted acetone is rectified and returned to the process, and
the by-product gas is scrubbed to remove its partial pressure of acetone and unreacted keten, the
feed acetic acid being used as scrubbing liquid.
It was not considered necessary to include plant for the distillation of the crude anhydride,
as this process is fairly straightforward and could be assessed much more economically in the
laboratory. ,
The preheating and cracking tubes were constructed of solid-drawn 25/20 chromium-nickel
steel of I in. nominal diameter. This material was selected for its good thermal and mechanical
properties, which are necessary in the construction of a large-scale cracking unit. It was thought
!
that the copper tubes used in the published work would be quite unsuitable for the plant scale;
silica is also a most undesirable structural material and the nickel-free irons of the Sicromal type
suffer from the disadvantage of great brittleness, which makes fabrication and support design
I
difficult. High mass-velocities in the range 10-30 ft.1b.sec. units were employed to give relatively

J. appl. Chern., 3, June, 1953

--------- 1_

 DAROUX-PRODUCTION OF ACETIC ANHYDRIDE

CRUDE
GAS

GAS
SEPARATOR

ACETONE
VAPORIZER
REC~CLE
ACETONE

CRACKER ABSORBER
FEED PUMP TOWER

,-----------IG---+-----...---------.L--~FEED ACETONE

CRUDE PRODUCT

FIG. 3. Outline flour-sheet of pilot plant for acetone cracking

short contact-times and high productivity. High vapour-speeds also provide sufficient kinetic
energy to scour the tube free from by-product coke. •
Initial operation of the pilot unit was hampered by excessive formation of coke, which quickly
blocked the comparatively small tube. In some cases this coke was removed by steam and air
purging. When the blockage was very severe, it was necessary to take out the tube and remove
the coke mechanically. It was found that new 25/20 tubes give almost 100°" conversion of the
acetone into hydrogen and carbon, but that after some time they become conditioned, so that the
dehydrogenating character of the metal surface is gradually reduced. It reappears, however, after
a tube has been purged with steam and air. Such a method of operation would obviously be too
uncertain for full-scale plant working; subsequent work by Tyler led to the discovery that the
addition of very small amounts of carbon disulphide to the acetone feed almost completely inhibited
the dehydrogenation reaction."
Three months' intensive pilot-plant operation sufficed to give the hasic design-data for the
consideration of a full-scale process. The important relationship between the selectivity and
conversion per pass was then well established and it was satisfying to find that both the weight
balances and the gas analyses and volume gave a good correlation. It had been thought that minor

90r---.,.--------,---------,

.c,

~ 80

....
u
~ I
~ 70 - ; - ---l__ --- _
z .
UI
....
UI

"
I
10 15 20 25 30
ACETONE CONVERSION. per cent

FIr;. 4. Conuersion-solccriricy relation for acetone cracking

impurities might build up in the recycle acetone during continued operation, but careful fractionation
of the material failed to reveal any important accumulation, though, after continued recycling, the
0
acetone had a I' ;, (molar) oxygen demand from acid permanganate at 86 F.

J. appl. Chcrn., 3, June, 1953

 DAROUX-PRODUCTION OF ACETIC ANHYDRIDE

Owing to the urgency of the project, the pilot plant was built in the United States by arrangement
with a leading oil company, and it is a pleasure to recall the harmonious co-operative atmosphere in
which the work was carried out.
Ii

Selectivity, conversion and gas analysis P

S
The general selectivity-conversion relationship for acetone-cracking to keten is shown in Fig. 4, 11
which shows the trend of the data. It is not, however, claimed that the yields and operating data 11
of the full-scale plant are precisely defined by this graph. It is interesting to derive the selectivity S
and conversion from the gas analysis and gas volume. These variables are usually much more
quickly and easily measured on a plant than the overall mass-balance. I
Consider a typical gas analysis from the thermal decomposition of acetone at about 100: j

conversion, given in Table 1.

e
Table I v
f
Gas analysis from acetone decomposition: pilot plant run 17B mass velocity, t
21 ft.lb.sec. units; contact time, 0'40 sec. C
% (v jv) c

Carbon dioxide
Unsaturated hydrocarbons 3'7
Carbon monoxide II ·8
Hydrogen 1·6
Methane 82'5

100'0

Moles of gasfmoles of feed .. o- Il6

The methane and hydrogen in the gas have obviously arisen from the thermal decomposition
of the acetone according to the primary reaction CH 3·CO·CH;l·0>- CH 4 + CH 2:CO, and the
dehydrogenation reaction CH 3 · CO· CH 3 -'~ 3H z I CO -1- 2C; the conversion of the acetone, that
is the number of moles of acetone decomposed, as a percentage of the number of moles of acetone
fed, is:
Moles of (methane + o- 33 hydrogen) produced
-~~~--~~_._---~- . -~X 100
Moles of acetone fed
or, for this particular case, 0'Il6 X 0·83 X 100 = 9'6%. A weight balance gave 9'5%.
The selectivity to keten, that is the percentage of the acetone decomposed that produces a
useful product, requires more careful evaluation. Considering the components of the gas in turn,
carbon dioxide can arise only by a useless reaction which need not be postulated, but which must
involve two molecules of acetone; unsaturated compounds and carbon monoxide, which should
theoretically be in the ratio I: 2, come from the undesirable thermal decomposition of keten; and
hydrogen arises from the slight dehydrogenation of the acetone.
Expressed as a ratio, this gives:

Selectivity = Moles~facetone~eco~p()s~=...rn~les of ac~oI1e...llSelesslL~ac~dX 100

Moles of acetone decomposed

~ (CH 4 -+- ~i~!:!zL~ICO_,,-:,,~.0 X 100

CH 4 + 0'33 H z

which for the particular case gives

0.830 - o· 126
Selectivity X 100
0·83°
85'8%

J. appl. Chern., 3, June, 1953

 DAROUX-PRODUCTION OF ACETIC ANHYDRIDE 245

The weight balance gave a selectivity of 82' 2~6, which, of course, includes the loss of some
liquid product as polymers of keten.
The interpretation of the gas analyses has proved most useful in studying the course of the
pilot-plant reactions, particularly in the initial stages, when dehydrogenation occurred with a keten
selectivity of only 1 or 2% and the hydrogen selectivity was about 98%. There are of course
minor deficiencies and inconsistencies in the gas-analysis figures. For example, the carbon
monoxide: unsaturated ratio is never exactly 2 as the chemical equation requires, but the overall
scheme showing the competing reactions is sound enough for practical purposes.

Full-scale plant design

The full-scale plant design involved as a first step several tentative calculations for the most
economical unit. The variables were the conversion-selectivity relationship established by pilot
work, the estimated plant cost for units having different conversions per pass, and the predicted
future cost of acetone. The higher the price of acetone in relation to plant costs, the lower was
the conversion that could be allowed to give an economical product. The unit was eventually
designed for a conversion of 25% per pass for maximum output. Lower outputs could then be
obtained, if desired, with enhanced chemical efficiency.
The overall flow-sheet of the process, as adapted for a full-scale plant, is shown in Fig. 5.

ACETIC ACID

~~.
GAS-SCRUBBING
SY5 TEM

, STRIPPING
I STill

FIG. 5. Basic flow-sheet for production of acetic anhydride

This shows the cracking furnace, quenching unit, condenser absorbers, gas-scrubbing plant
and distillation units in the most elementary form.
After the leading dimensions of the units, as fixed by the overriding economic conditions, had
been decided, the main technical problems were: (a) furnace design, (b) condensing and absorption
equipment and (c) distillation of the recycle and product streams. These are discussed below.

(a) Furnace design

The problem of designing a cracking furnace to operate under the desired conditions of close
temperature-control, reasonable thermal economy, low pressure-drops and flexible operation, is
a very common one for the oil-refining engineer, and there are almost as many types of gas-phase
thermal cracking furnaces as there are designers. The cracking of acetone had, however, two
special features which required more than usual emphasis. First, the feed stock is an extremely
high-priced one, and hot acetone is a most searching material in finding leaks through jointed tubes.
Secondly, the plant was to be geared to the needs of a very costly works, where any interruption
of anhydride supply would be extremely expensive, if not catastrophic, so that immediate replacement
of a split or faulty cracking tube was imperative.
A review of the available types of furnace did not disclose a standard unit exactly suited to

J. appl. Chem., 3, June, 1953

 DAROUX-PRODUCTION OF ACETIC ANHYDRIDE

our needs and so the design of yet another type of furnace was undertaken. The general layout this reasc
is shown in Fig. 6. provides
mean pos
on the tu
Flue
PREHEATING
CELL
the come
one of w
to 4000]
supporte
are exhai
the conv:
The
in Fig. 6
, :
;,
"

"

"

-~

(b) Cond
One
possible
the crael
excess 0
expansic
consider
expansic
quench
FIG. 6. Diagrammatic view of fum ace tubes.
Val
acetone,
The unit consists of two identical circular cells, each designed to accommodate a 25/20 combiru
chromium-nickel welded solid-drawn coil about 400 ft. in length. Built into the walls of each cell The es
of the furnace are 24 wedge-shaped ledges which mate with lands on the eight coil-supports. Each exercise
of these supports is built up from standard alloy-steel castings in three sections which are pin-jointed the des
for flexibility. In this way the whole coil is allowed to float in the cell to avoid any stress due to He
thermal expansion. The first cell is used to preheat vaporized acetone to the incipient cracking as it ws
temperature. The firing of the second coil is varied to give the desired degree of conversion. of shell
The cells are capped by sand-sealed refractory domed lids which support the four burners firing Tl­
each cell. Dual burners are employed and steam-atomized distillate oil is used for starting up acetic a
the unit; when gas production has been stabilized, the oil stems are withdrawn and inspirator gas keten.
burners are used. acetic ~
Lobo & Evans have shown, in their invaluable paper.t" the great advantage of a high ratio of temper
refractory area to furnace volume in obtaining good radiation coefficients in direct-fired furnaces. For effluent

J. appl. Chem., 3, June, 1953 J. app

 DAROUX-PRODUCTION OF ACETIC ANHYDRIDE 247

this reason the circular cells have been divided into four sections by a battered cruciform wall which
provides a good focus for flame radiation. The angle of inclination of the burners is variable, the
meanposition being about 5° from vertical, facing towards the wall, so preventing flame-impingement
on the tubes.
Flue gases from the cracking cell join the products of combustion in the preheating cell and
the combined gases then pass to a convection section consisting of two sets of banked finned tubes,
one of which is used to vaporize the feed. A second bank takes the flue-gas temperature down
to 400° F. in preheating the feed to the acetone-distillation unit. The connecting bends are
supported in davits with counterweighted wire ties to take up expansion strains. The flue gases
are exhausted through a hot-gas fan to the stack, and the usual by-pass flues are provided to isolate
the convection section or any cell, and run on natural draught.
The overall thermal efficiency of the furnace is about 85°;,. A diagrammatic view is shown
in Fig. 6. A view of the installation is given in Fig. 7.

FIG. 7. Cracking furnace showing quench unit in foreground

(b) Condensing and absorption equipment

Once keten has been formed in the cracking unit it is very important to quench it as quickly as
possible to prevent its thermal decomposition to ethylene and carbon monoxide. For this reason
the cracked outlet gases are shock-cooled by injection of one of the recycle streams containing an
excess of acetic acid. A simple four-jet unit is employed for this and an immediate volume
expansion takes place on partial vaporization of the quench feed. The pipeline is therefore
considerably expanded at this point and the severe thermal strain is taken up by generously-sized
expansion bellows. A single equilibrium contact is then given in a packed tower over which liquid
quench is circulated, with continuous filtration to remove suspended coke blown from the cracking
tubes.
Vapour at about 300c F., leaving the so-called quench tower, and containing permanent gas,
acetone, acetic acid, acetic anhydride and keten, is then condensed. During the condensation,
combination of the keten with acetic acid takes place to form anhydride, with the evolution of heat.
The estimation of condenser surface to deal with this poly-component gas mixture was a nice
exercise in chemical engineering calculation. A trial and error step-wise method was evolved for
the design and this was checked on a very small laboratory unit to give a basis for specification.
Here, as at other points in the plant, Rosenblad spiral-plate exchangers were successfully used,
as it was found that the cost per equivalent square foot of stainless-steel surface was less than that
of shell-and-tube or battery-type units.
The cracker products now separate into a crude liquid fraction containing the bulk of the
acetic anhydride, and a gas stream containing a high concentration of acetone and some unabsorbed
keten. The gas is therefore first scrubbed with a substantially acetone-free recycle stream containing
acetic acid. A normal bubble-cap tower is used for this duty, but in order to keep the operating
temperature low, internal recirculation through water-cooled Rosenblad exchangers is used. The
effluent gas from this tower contains a little acetone, which is effectively removed by contact in a

J. appl, Chern., 3, June, 1953

 --- ~ ----=----=--- - - ­

DAROUX-PRODUCTION OF ACETIC ANHYDRIDE

second tower through which flows the acetic acid feed to the plant. The gas is now saturated
with acetic acid, which is removed by water scrubbing, and the aqueous acetic acid is returned to
the acetate unit for concentration. A final caustic wash is given before the gas passes to the holder
for storage as furnace fuel.

(c) Distillation of recycle and product streams

The equipment is designed on normal lines, though it was necessary to check all vapour-liquid
equilibria and thermal data in the laboratory before preparing final designs. An acetone still
produces recycle acetone from the crude product and this overhead distillate passes back to the
furnace. The low conversion makes the duty of the still relatively heavy and some thermal
economy is achieved by preheating the feed in the convection section of the furnace. Also, as the
feed rate is high in comparison with the overhead, the trays are split below the feed plate to
accommodate the high liquid rates. The construction is entirely in stainless steel and much
ingenuity has been exercised by E. W. Fletcher in designing the tray supports and structure to
give maximum economy in material and very good standards of accuracy in the plate levelling.
The base product from the acetone still is cooled in a Rosenblad exchanger and used as the
recycle feed to the quench unit and first gas-scrubber. A side stream passes forward for stripping
to give an overhead of acetic acid and acetone and a bottoms product of strong anhydride and
high-boiling polymers. This is distilled in a final column to give an overhead of acetic anhydride
and a small residue of tarry compounds. In view of the unknown nature of these products it was
considered desirable to fit this distillation unit with duplicate re-boilers arranged with valves, so
that the spare could be cleaned without interruption of production.
The condensers for all the fractionating columns are of the spiral-plate type, and we have found
them most suitable for their duty; in addition to relatively low cost, they have high heat-transfer
coefficients and low pressure-drops.

Standardization
As far as possible, plant units have been standardized to reduce to the minimum the necessary FIG.
stocks of spares. The cracking and preheating coils, the most expensive individual items, are Prelimil/ary mOG

identical, and the spares are therefore interchangeable. All the liquid exchangers are of the same
pattern. Stainless-steel circulating pumps, of which there are 26, have been divided into three
standard design groups, and the storage tanks, valves and pipelines have been reduced to standard
sizes even where this has meant slight over-design, to allow rapid replacement from economically
small stocks. This is particularly important with high-priced stainless-steel equipment in a new
project where there may be unexpectedly high corrosion-rates.

Layout
After the major items of equipment have been designed, their disposition in the plant area
becomes the major problem, and inexpensive rough models were found to be most effective in
helping the visualizing of the appearance and convenience of the finished plant. This was
particularly true of the pipe runs, which became complicated with a recycling process. The
pipelines were simulated on the finished model by the piping contractor, who used different colours
of insulated wire to represent the pipe sizes and indicated valves by simple paper-fasteners clipped
to the wires. In this way it was possible to simplify and make more economical many of the
process pipes. Two views of the models are shown as Figs, 8 and 9.
The general aim in the layout was to use structural members as supports for simple sheeting
to give shelter at the focal points. Fire walls, fitted with steel partition doors, were used on one
side of the furnace building, and the corresponding face of the pro:ess building was built as an
almost blank wall to give additional protection. The storage tanks of highly inflammable materials
were located on the side of the process building remote from the furnace.
As far as possible, most of the process pumps were sited together in a single gallery (Fig. 10)
to allow easy access for packing and general maintenance, and this also simplified the installation
of a ventilated pump-drip collection system, returning leakages to the crude-product storage tank.
This is very necessary with lachrymatory materials like acetic acid and acetic anhydride.

Instrumentation
The plant is almost completely automatically controlled. A central control room, slightly
pressurized with fresh air, provides the focal centre for plant operation, and there are few plant­
variables that cannot be observed and corrected in the control room.

J. appl, Chem., 3, June, 1953 J. appJ

 DAROUX-PRODUCTION OF ACETIC ANHYDRiDE 249

FIG. 8 (left).
Preliminary model of furnace room and
annexe

FIG. 9 (right).

Preliminary model of pr ccess building

(left).

FIG. 10
Pump gallery

J. appl, Chem., 3, June, 1953

 DAROUX-PRODUCTJON OF ACETIC ANHYDRIDE

Furnace firing is controlled by selected thermocouple points in the preheating and cracking
cell.
A generous allowance of spare thermocouples was made at critical points in the vapour stream
and this has proved well worth while in practice. At the more important points we have fitted six
thermocouples, and the main temperature recorder and controllers automatically select the surviving
couples.
Burner trimming and air adjustment are done manually at infrequent intervals. Duplicate
hand-operated and manually-controlled air-operated valves are provided in the furnace room for
emergencies, and these are useful when the plant is being started up. Oil-firing is done under hand
control.
Feeds to the cracking furnace, scrubbing towers and distillation units are regulated automatically
with pneumatic control systems, usually operating through transmitting' flowrators '. A few orifice
plates are used on gas lines and hot-liquid feeds. Each of the control valves is provided with a
hand-operated by-pass, and, where possible, the corresponding' flowrator ' is conveniently sited so
that the operator can see the flow changes if he should have to leave the control room and go over to
hand operation.
Distillation-process temperatures, which guide the automatic reflux controllers, are measured
by gas-filled bulbs and transmitted to the controllers and records pneumatically. Instrument
supply is provided by a Nash pump on the plant, with an automatic switch to cut in the works air
in the event of failure.
The instruments in the control room were arranged on a diagrammatic flow-sheet panel after
much discussion, and operating experience has shown the advantage of this scheme in giving the
operator a clear picture of the plant conditions. By using miniature instruments, a well spaced this is 111
layout can be obtained, with very slight sacrifice of chart accuracy. Fig. I I shows a general view product
of the control room. working
gives a.

Safety
Tt
acetic a
Fi
foam r
fires c(
FIG. I r. instant
General view of control r,JQIII tank is
spindle
tank, j
the fu
of the
acetOl
i
flame
pumI
foren
Process temperatures, other than those recorded, are measured at a desk indicator with three
24 point banks of selecting switches. When a temperature is selected for measurement, a signal only
light appears on the flow-sheet panel, showing the location of the point whose temperature is being requ
indicated. with
Audible and visible alarms are fitted at all critical points and come into action for important sup:
pump-failures, flow-failure, high or low levels in any process vessel, higher-than-scheduled COUI
temperatures in the preheater or cracker cell, or unusually high gas-pressure in the scrubbing
system.
Op
Other instruments include a gas specific-gravity recorder, continuous gas-analyser, pneumatic
tank-stock indicators, and integrators for power, steam, water, raw material and finished product.
ter:
Routine instrument maintenance on small parts is done in the control room behind the control
panel. Major repairs on control valves are of course done in the workshop.
she
Our experience so far has been that full instrumentation and control have been well worth while.
The advantages lie rather in precision of the operating variables than in major savings in labour cost. in
On the plant a large enough operating crew must always be available to cope with emergencies, and tel

J. appl. Chern., 3, June, 1953 J.

 I .

,I

DAROUX-PRODUCTION OF ACETIC ANHYDRIDE

FIG. 12.
View behind control panel

this is more than the labour needed for plant running. With a plant producing a relatively expensive
product, steady operating conditions, maintained with the least amount of tediousness in day-to-day
working, leave plenty of scope for concentration on increased yields and better efficiencies. This
gives a real boost to the productivity of the labour employed.

Safety
The main plant-hazards are fire and risk of injury from the very reactive chemicals, keten,
acetic acid and acetic anhydride.
Fire precautions include a foam dowsing-system for the two 400-ton acetone tanks, and a
foam manifold for general use. Experiments with artificial acetone fires showed that for open
fires copious dilution with a water spray is most effective, and water screens can be turned on
instantly from any floor of the process building to protect the stairways. A steam-purged dump
tank is provided at the furnace outlet and the valves are operated from floor level with extended
spindles. These valves are checked regularly as a routine. Excess pressure is also vented to this
tank, in which about 1000 gallons of water are held to give dilution. The quantity of acetone in
the furnace and tubes under normal operating conditions is relatively small, owing to the low density
of the high-temperature vapour, but steam dowsing of the furnace and four ways of shutting off the
acetone feed from safe positions have been installed.
A direct line connects the plant to the works fire-station in case of emergencies. Naturally,
flame-proof electrical equipment has been used wherever acetone vapour or gas may leak. All
pump starters are clearly labelled, and a flicker of the alarm light in the control room shows the
foreman which pumps have been started up.
Keten itself has been reported to be highly toxic, but fortunately it is so reactive that there is
only a slight risk of free keten escaping from the plant in any appreciable concentration. The main
requirements for personal safety are good ventilation, free accessibility of the plant units, and,
with dangerous operations, a proper supply of protective goggles, gloves and clothing, and
supervision to see that these are fully used. The usual safety showers and eye douches are of
course provided.

Operating results
As the plant has only recently begun to operate, it would be premature to discuss the long­
term operating results.
We have confirmed a remarkable sensitivity of gas-make to operating temperature. This was
shown by the pilot plant, but is much more marked on the full-scale unit. When a small change
in the set point of the cracker-outlet temperature is made, the gas-make changes long before the
temperature change is noticed, and during normal operation, where the temperatures are usually

J. appl. Chern., 3, June, 1953 F~

 DAROUX-PRODUCTION OF ACETIC ANHYDRIDE

held to within 1° F., slight ripples in the gas-make chan show minor temperature variations in the
cracking coil. I. ARYLO
As the plant was completely new in our works experience, we thought it desirable to give
qualified shift supervision for the first four operating weeks after routine testing and furnace HALOGEN
drying-out. The shift chemical engineers did their training job so well that we were glad to hand
the unit over to the shift foremen after this period, and we are very pleased with their handling of
this complicated plant. B

Sodium at
proportions of
hours at 200-2
phenols. Sod

General introd1
The work de
of the well know
acidic carboxyl f
FIG. 13. amide (IV) grou
General view of the plane O'CH,
ACl
\ II
~/
CI
(I)
It was not expel
but the sulphir
might well COD
sulphinic analo
Acknowledgments growth-regulatl
sequent develo
The author would like to pay tribute to the engineers and chemists who have formed the of the type SOl
design team. In particular he acknowledges with gratitude the major pan played by the chief simulate the ac
acetate engineer, Mr. E. Turney, in the successful implementation of the project. The work done remains, there!
by his assistant, Mr. E. W. Fletcher, has contributed very largely to producing a successful However,
mechanical design and layout. tion of the suI
The instrument engineers, Messrs. E. W. Little and W. Hibbert, have met our most exacting conventional c
requirements for process control. The construction was in the hands of Mr. W. Ellard, who built phenoxr meth:
the plant in a very short time under difficult conditions, and Mr. D. L. Tyler's fundamental work insectICIdes, C
in the chemistry and physical data of the process has been the essence of the full-scale design. groupS of oH
Finally, the author is glad to acknowledge the help of his friend and colleague Mr. J. D. Smith,
who has spent so much of his time on the plant design and operation. Aryloxymel
The author'S thanks are due to the directors of Courtaulds Ltd. for permission to publish this AryloxyJ
paper. described in .
HO·CHz·SI
Courtaulds Ltd.
hydroxymetl
Research Department (Chemical Engineering Section)
acid itself re
Coventry
existence in
Received '-7 February, 1953 The n
sulphonates
no details t<
References sulphonate:
1 Zakal, H. W., Chem, Ind., Philad. 1948, 63, 209 6 Peytral, E., Bull. Soc. chim, Pr., 1921,31, [iv], 122 thioethan el
phenols5 t
, Loveless, L. W. J., Trans. lnstn chem. Engrs, Land.,
7 Hinshelwood, C. N. & Hutchison, Proc, roy. Soc., bisulphite,
1947, ~-7, 47 1926, [A] III, 245
of sodium
3 Schmidlin, J. & Bergmann, M., Ber, dtsch, chem.
2-hydroxy
Ges., 1910,43,2821 • Taylor, H. S., J. phys. Chem., 1926, 30, 1433
not to the
• Rice, F. 0., Greenberg, J., Waters C. E. & Vollrath, John:
, Courtaulds Ltd. & Tyler, D. L., B.P. 629,2II
R. E., J. Amer. chem, Soc., 1934, 56, 1760 sodium f
• Hurd, C. D. & Tallyn, W H. J. Amer. chem, Soc., 10 Lobo, W. E. & Evans, J. E., Trans. A mer. Inst, halogen a
192 5, 47, 1427 chem. Engrs, 1939, 35, 743 bound 3I

J. appl. Chem., 3, June, 1953 ]. appl.